β,β-Dicyano styrenes

ABSTRACT

The present invention relates to para-substituted-amino-β,β-dicyano styryl disperse dye compounds having an acyloxy group in an ortho position to the methine group.

IMPROVEMENTS IN OR RELATING TO ORGANIC COMPOUNDS

The present invention relates to styryl compounds, their production anduse.

In particular, the present invention provides disperse dyes beingpara-substituted-amino-(β,β-dicyano)styryl compounds which have anacyloxy group in an ortho position to the methine group.

By `acyl` is meant (C₁₋₆) alkoxycarbonyl, chloro- or bromo (C₁₋₆)alkoxycarbonyl, (C₁₋₆) alkoxy (C₂₋₆)-alkoxycarbonyl, phenyl (C₁₋₆)alkoxycarbonyl, phenoxycarbonyl, (C₁₋₆) alkylsulphonyl, (C₅₋₆)cycloalkylsulphonyl, phenyl (C₁₋₆) alkylsulphonyl, (C₁₋₆) alkyl- or di-(C₁₋₆) alkylamino-carbonyl, (C₁₋₆) alkyl- or di- (C₁₋₆)alkylaminosulphonyl, N-(C₁₋₆) alkyl-N-phenylamino-carbonyl or-sulphonyl,and radicals of formula ##STR1## in which R signifies the atomsnecessary to form, with the nitrogen atom, a morpholine, thiomorpholine,pyrrolidine or piperidine ring,

Any phenyl moiety in such radicals being unsubstituted, monosubstitutedby ethoxy or substituted by up to two substituents selected from thegroup consisting of chlorine, bromine, methyl and methoxy. Acyloxy is tobe understood accordingly.

Apart from the acyloxy group ortho to the methine group, the benzenenucleus may be further substituted. Any substituents on the amino groupin the compounds of the invention are preferably unsubstituted orsubstituted alkyl or cycloalkyl or are such as to form, together withthe nitrogen atom, a hetrocyclic ring. As will be appreciated, thesubstituents will be so chosen as not deleteriously to affect thecompounds' utility as disperse dyes, particular examples of suitablesubstituents being hereinafter given.

More particularly the present invention provides compounds of formula I,##STR2## in which R₁ signifies (C₁₋₆) alkyl or (C₅₋₆) cycloalkyl,

R₂ signifies (C₁₋₄) alkyl; or (C₁₋₄) alkyl monosubstituted by chlorine,bromine, phenyl, phenoxy, (C₁₋₄) alkoxy, (C₁₋₄)alkoxycarbonyl,(C₁₋₄)alkylcarbonyloxy, (C₁₋₄) alkoxycarbonyloxy or benzoyloxy,

Or R₁ and R₂, together with the nitrogen atom to which they are bound,form a pyrrolidine, piperidine or morpholine ring, and

R₃ signifies hydrogen,

Or R₃,together with R₁ forms a pyrrolidine or piperidine ring,

R₄ signifies (C₁₋₆)alkoxycarbonyl, chloro (C₁₋₆)alkoxycarbonyl, bromo(C₁₋₆)alkoxycarbonyl, (C₁₋₄) alkoxy (C₂₋₆) alkoxycarbonyl,benzyloxycarbonyl, phenoxycarbonyl, (C₁₋₆) alkylsulphonyl, (C₅₋₆)cycloalkylsulphonyl, benzylsulphonyl, di(C₁₋₄)alkylaminocarbonyl,N-(C₁₋₄) alkyl-N-phenylaminocarbonyl, di-(C₁₋₄) alkylaminosulphonyl,N-(C₁₋₄) alkyl-N-phenylaminosulphonyl or ##STR3## in which R₅ signifiesthe atoms necessary to form a pyrrolidine, piperidine or 4-morpholinering,

any phenyl moiety in such substituents R₂ and R₄ being unsubstituted orsubstituted by up to two substituents selected from the group consistingof chlorine, bromine, methyl and methoxy or monosubstituted by ethoxy,compounds in which such phenyl moiety or moieties are unsubstitutedbeing preferred.

Any alkyl radical as R₁ is preferably (C₂₋₄) alkyl, in particular ethyl.Preferably, R₁ signifies alkyl.

Any substituted alkyl as R₂ is preferably monosubstituted by chlorine,bromine, methoxy, ethoxy, phenyl, phenoxy, acetoxy, propionyloxy,(C₁₋₄)alkoxycarbonyl or (C₁₋₄)alkoxycarbonyloxy.

Any substituted or unsubstituted alkyl radical as R₂ is preferably C₂₋₄,in particular ethyl, except where R₂ is alkyl substituted by phenylwhere such alkyl radical preferably contains 1 to 4, more preferably 1or 2 carbon atoms.

R₂ is preferably an unsubstituted or substituted alkyl radical. Morepreferably R₂ is (C₂₋₄)alkyl; (C₂₋₄) alkyl monosubstituted by chlorine,bromine, methoxy, ethoxy, phenyl, phenoxy, acetoxy, propionyloxy, (C₁₋₄)alkoxycarbonyl or (C₁₋₄) alkoxycarbonyloxy; or benzyl. Even morepreferably R₂ is (C₂₋₄) alkyl, especially ethyl, which is unsubstitutedor monosubstituted by acetoxy, propionyloxy, methoxycarbonyl,ethoxycarbonyl, methoxycarbonyloxy or ethoxycarbonyloxy. Most preferablyR₂ signifies unsubstituted (C₂₋₄) alkyl,especially ethyl.

R₃ is preferably hydrogen.

Any alkoxycarbonyl or alkylsulphonyl radicals as R₄ preferably containup to 4 carbon atoms and any cycloalkyl radical is preferablycyclohexyl.

Preferably R₄ signifies (C₁₋₄) alkoxycarbonyl, chloroethoxycarbonyl,bromoethoxycarbonyl, methoxyethoxycarbonyl, ethoxyethoxycarbonyl,dimethyl- or diethylaminocarbonyl, benzyloxycarbonyl, (C₁₋₄)alkylsulphonyl, (C₅₋₆) cycloalkylsulphonyl, dimethyl- ordiethylaminosulphonyl, benzylsulphonyl, piperidinocarbonyl,morpholinocarbonyl, pyrrolidinocarbonyl, piperidinosulphonyl,phenoxycarbonyl, morpholinosulphonyl or pyrrolidinosulphonyl. Morepreferably, R₄ signifies (C₁₋₂) alkoxycarbonyl, benzyloxycarbonyl,phenoxycarbonyl, (C₁₋₄) alkylsulphonyl, cyclohexylsulphonyl,benzylsulphonyl, piperidinocarbonyl, pyrrolidinocarbonyl,morpholinocarbonyl, morpholinosulphonyl, pyrrolidinosulphonyl,piperidinosulphonyl or dimethyl-or diethylaminocarbonyl or -sulphonyl.Even more preferably, R₄ signifies (C₁₋₄) alkylsulphonyl,benzylsulphonyl or cyclohexylsulphonyl, with (C₁₋₄) alkyl sulphonylbeing most preferred.

Preferred compounds of formula I are those of formula Ia, ##STR4## inwhich R₆ signifies (C₂₋₄) alkyl,

R₇ signifies (C₂₋₄) alkyl which is unsubstituted or monosubstituted by(C₁₋₂) alkylcarbonyloxy, (C₁₋₂)alkoxycarbonyl or(C₁₋₂)alkoxycarbonyloxy,and

R₈ signifies (C₁₋₂) alkoxycarbonyl, benzyloxycarbonyl, phenoxycarbonyl,(C₁₋₄) alkylsulphonyl, cyclohexylsulphonyl, benzylsulphonyl,piperidinocarbonyl,morpholinocarbonyl, pyrrolidinocarbonyl,pyrrolidinosulphonyl, piperidinosulphonyl, morpholinosulphonyl, di-(C₁₋₂) alkylaminocarbonyl or di- (C₁₋₂) alkylaminosulphonyl.

More preferred compounds of formula I are those of formula Ib, ##STR5##in which R₉ signifies (C₁₋₄) alkylsulphonyl, cyclohexylsulphonyl orbenzylsulphonyl.

The present invention also provides a process for the production ofpara-substituted-amino-(β,β-dicyano) styryl compounds of the presentinvention, as defined above, comprising condensing the correspondingaminobenzaldehyde or a (C₁₋₄)alkylimino or quaternated (C₁₋₄) alkyliminoderivative thereof with malonic acid dinitrile, preferably in a 1:1molar ratio. For example the compounds of formula I, can be prepared bycondensing a compound of formula II, ##STR6## in which R₁ to R₄ are asdefined above,

R₁₃ is oxygen, ═NR₁₄ or ═NR₁₄ R₁₅ in which R₁₄ is (C₁₋₄)alkyl, and R₁₅is (C₁₋₄)alkyl or phenyl,

with malonic dinitrile.

The condensation reaction may be effected using Knovenagel conditions.Suitably, the reaction is conducted in the presence of an organic basein an inert protic, preferably anhydrous,solvent. Suitable solventsinclude ethanol and methanol.

As examples of suitable organic bases may be given piperidine,pyrrolidine, pyridine, triethylamine and triethanolamine.

The reaction is suitably conducted at a temperature in the range of from50° to 150° C., preferably at the boiling point of the solvent used. Thecompounds according to the invention usually precipitate during thereaction or on cooling; if not they may be obtained by concentrating,cooling and filtering.

Preferably, malonic acid dinitrile is condensed with the correspondingbenzaldehyde.

The starting materials are produced in accordance with known methodsfrom available starting materials, for example by condensing thecorresponding 3-aminophenols with an acid anhydride or chloride andforming the aldehyde employing Vilsmeyer reaction conditions.

The compounds according to the invention are disperse dyes and may beused to dye substrates consisting of or comprising semi-synthetic orsynthetic, hydrophobic, high-molecular weight organic substances.Examples of suitable substrates which may be dyed are those consistingof or comprising linear aromatic polyesters, cellulose 21/2 acetate,cellulose triacetate and synthetic polyamides.

The compounds according to the invention may be converted into dispersedyeing preparations according to conventional methods, for example bygrinding in the presence of dispersing and/or filling agents, andoptionally dried in a vacuum or by spraying. The preparations may beused as such, or after the addition of water, for pad dyeing,exhaustdyeing or printing from a long or short bath. Dyeing or printing may becarried out in accordance with known methods.

The compounds of formula I, as defined above are also suitable for theso called heat transfer printing process of textiles. In which case, thecompounds of formula I are formulated into suitable printing inks orpastes in known manner and are printed onto a temporary support e.g.paper, for application to the desired substrate in conventional manner.Suitable substrates which may be printed by the transfer printingprocess include linear,aromatic polyesters, cellulose 21/2 acetate,cellulose triacetate and synthetic polyamides.

The dyeings obtained have especially notable light fastness. They alsohave notable wash, perspiration and rubbing fastness. The dyes areresistant to the effect of reduction when dyeing polyester-wool blends.The dyes reserve wool and cotton and possess notable levelling andthermomigration properties.

The following Examples further served to illustrate the invention. Inthe Examples all parts are by weight and all temperatures in degreesCentigrade.

EXAMPLE 1

15 Parts 2-n-butyl-sulphonyloxy-4N,N-diethylaminobenzaldehyde, 3.2 partsmalonic acid dinitrile and 0.1 parts piperidine are dissolved in 20parts anhydrous ethanol, brought to the boil over the course of 2 hoursunder reflux,and subsequently allowed to cool to room temperature. Thecondensation product of formula ##STR7## is filtered off and washed witha little methanol. After re-crystallisation from an n-butanol/benzenemixture, yellow crystals with a melting point of 104°-106° are obtained.

2-n-butyl-sulphonyloxy-4-N,N-diethylamino-benzaldehyde can be producedas follows:

40 Parts dimethyl formamide are cooled to 0°, 21 parts phosphorusoxychloride are added with cooling over the course of 30 minutes and themixture is then stirred for 30 minutes at 0°. A solution of 39 parts3-n-butylsulphonyloxy-N,N-diethylaniline in 10 parts dimethyl formamideis added thereto over a period of 15 minutes, the reaction mixture isheated to 40° and kept at this temperature for 5 hours. The reactionmixture is then discharged into 900 parts of an ice/water mixture,adjusted to a pH of 5 with sodium acetate and stirred overnight at roomtemperature. Subsequently, it is taken up in an ethyl acetate/diethylether mixture, separated from the aqueous phase,washed out withdistilled water, dried over Na₂ SO₄ and freed from solvent byevaporation.

3-n-butyl-sulphonyloxy-N,N-diethyl aniline can be produced as follows:

A solution of 50 parts 3-N,N-diethylaminophenol in 80 parts acetone and200 parts water is adjusted to a pH of 12 with sodium hydroxide. Asolution of 52 parts n-butane-sulphonyl chloride in 260 parts acetone isthen added, with stirring, over the course of 1 hour whilst keeping thepH constant by the addition of NaOH and ensuring that the temperaturedoes not rise above 30°. After stirring for a further hour at roomtemperature, the reaction mixture is divided between diethyl ether andwater; the organic phase is washed out with dilute sodium hydroxide andwith water, dried over Na₂ SO₄ and evaporated. The residue is distilledin a vacuum.

The following Table shows other dyes of formula I which can be producedin a similar way to that described in the above Example. The shadeobtained with these dyes on polyester fibre material is greenish-yellow.

                                      TABLE                                       __________________________________________________________________________    Example                                                                       No.  R.sub.2       R.sub.1       R.sub.3                                                                          R.sub.4                                   __________________________________________________________________________    (R.sub.1 & R.sub.2 are interchangeable when R.sub.3 = H)                       2   C.sub.2 H.sub.5                                                                             C.sub.2 H.sub.5                                                                             H  SO.sub.2 CH.sub.3                          3   "             CH.sub.2 C.sub.6 H.sub.5                                                                       "                                          4                                                                                  ##STR8##     C.sub.2 H.sub.5                                                                             H  "                                          5   C.sub.2 H.sub.5                                                                             "             H  CON(CH.sub.3).sub.2                        6   "             "             H  CON(C.sub.2 H.sub.5).sub.2                 7   "             CH.sub.2CH.sub.2CH.sub.2                                                                       SO.sub.2 CH.sub.3                          8   "             "             H  SO.sub.2(CH.sub.2).sub.3CH.sub.3           9   "             CH.sub.2CH.sub.2CH.sub.2                                                                       SO.sub.2CH.sub.3                          10   "             CH.sub.2 CH.sub.2                                          11   CH.sub.2 CH.sub.2OCH.sub.2 CH.sub.2                                                                       H  "                                         12   C.sub.2 H.sub.5                                                                             CH.sub.2 CH.sub.2 Cl                                                                        H                                                                                 ##STR9##                                 13   "             C.sub.2 H.sub.5                                                                             H  SO.sub.2 N(CH.sub.3)C.sub.6 H.sub.5       14   "             "             H  CON(CH.sub.3)C.sub.6 H.sub.5              15   CH.sub.2 CH.sub.2 OCOOC.sub.2 H.sub.5                                                       "             H  COOC.sub.2 H.sub.5                        16   C.sub.2 H.sub.5                                                                             "             H                                                                                 ##STR10##                                17   "             "             H  SO.sub.2C.sub.2 H.sub.5                   18   (CH.sub.2).sub.2 CH.sub.3                                                                   "             H  "                                         19   "             (CH.sub.2).sub.3 CH.sub.3                                                                   H  "                                         20   CH.sub.2 CH.sub.2C.sub.6 H.sub.5                                                            C.sub.2 H.sub.5                                                                             H  "                                         21   CH.sub.2 CH.sub.2OC.sub.2 H.sub.5                                                           "             H  "                                         22                                                                                  ##STR11##    "             H  "                                         23   "             (CH.sub.2).sub.3 CH.sub.3                                                                   H  "                                         24   CH.sub.2CH.sub.2CH.sub.2CH.sub.2CH.sub.2                                                                  H  "                                         25   CH.sub.2CH.sub.2OCH.sub.2CH.sub.2                                                                         H  "                                         26   C.sub.2 H.sub.5                                                                             C.sub.2 H.sub.5                                                                             H  SO.sub.2(CH.sub.2).sub.2 CH.sub.3         27   "             "             H  SO.sub.2(CH.sub.2).sub.3 CH.sub.3         __________________________________________________________________________    Example                                                                       No.  R.sub.1       R.sub.2       R.sub.3                                                                          R.sub.4                                   __________________________________________________________________________    28   C.sub.2 H.sub.5                                                                             C.sub.2 H.sub.5                                                                             H                                                                                 ##STR12##                                29   "             "             H  SO.sub.2(CH.sub.2).sub.4 CH.sub.3         30   "             "             H  SO.sub.2(CH.sub.2).sub.5 CH.sub.3         31   "             "             H                                                                                 ##STR13##                                32   "             "             H  SO.sub.2CH.sub.2 C.sub. 6 H.sub.5         33   "             "             H                                                                                 ##STR14##                                34   "             "             H                                                                                 ##STR15##                                35   "             "             H                                                                                 ##STR16##                                36   "             "             H                                                                                 ##STR17##                                37   "             "             H                                                                                 ##STR18##                                38   "             "             H                                                                                 ##STR19##                                39   "             "             H                                                                                 ##STR20##                                40   "             "             H                                                                                 ##STR21##                                41   "             "             H                                                                                 ##STR22##                                42   "             "             H                                                                                 ##STR23##                                43   "             "             H                                                                                 ##STR24##                                44   "             "             H                                                                                 ##STR25##                                45   "             "             H                                                                                 ##STR26##                                46   "             "             H                                                                                 ##STR27##                                47   "             "             H                                                                                 ##STR28##                                48   "             "             H                                                                                 ##STR29##                                49   "             (CH.sub.2).sub.3 CH.sub.3                                                                   H  SO.sub.2CH.sub.3                          50   "             "             H  SO.sub.2N(CH.sub.3).sub.2                 51   "             "             H                                                                                 ##STR30##                                52   (CH.sub.2).sub.3 CH.sub.3                                                                   "             H  SO.sub.2CH.sub.3                          53   "             "             H  SO.sub.2N(CH.sub.3).sub.2                 54   C.sub.2 H.sub.5                                                                             CH.sub.2 CH.sub.2C.sub.6 H.sub.5                                                            H   SO.sub.2CH.sub.3                         55   "             "             H  SO.sub.2N(CH.sub.3).sub.2                 56   "             CH.sub.2 CH.sub.2OC.sub.2 H.sub.5                                                           H  SO.sub.2CH.sub.3                          57   "             "             H  SO.sub.2(CH.sub.2).sub.3 CH.sub.3         58   "                                                                                            ##STR31##    H  SO.sub.2(CH.sub.2).sub.3 CH.sub.3         59   "             "             H  SO.sub.2N(CH.sub.3).sub.2                 60   "             "             H                                                                                 ##STR32##                                61   "             CH.sub.2 CH.sub.2 Br                                                                        H  SO.sub.2 (CH.sub.2).sub.3 CH.sub.3        62   "             CH.sub.2 C.sub.6 H.sub.5                                                                    H  SO.sub.2 C.sub.2 H.sub.5                  63   "             CH.sub.2 CH.sub.2 COOCH.sub.3                                                               H  SO.sub.2 N(CH.sub.3).sub.2                __________________________________________________________________________

application example a

10 parts of the dye obtained in Example 1 are ground together with 10parts dinaphthyl methane disulphonic acid sodium, 10 parts ligninsulphonic acid sodium, 30 parts water and 300 parts silica quartzitebeads until the average diameter of the dye particles is less than 1μ.The suspension is then filtered off from the silica quartzite beads andspray-dried under mild conditions.

1.4 Parts of the dye preparation thus obtained are added to 4000 partswater in a dye bath at 60° which has been buffered to a pH of 5 and themixture is stirred. 20 parts orthophenylphenol are added to the dyebathand 100 parts polyester fabric are dyed therein for 1 hour at 98°. Aftercooling, rinsing, soaping, further rinsing and drying, a deep yellowdyeing is obtained which is level and has notable fastness properties.

APPLICATION EXAMPLE B

30 Parts of the dye preparation prepared according to Example A aremixed well with 300 parts water. 600 Parts of a 4% aqueous solution oflocust bean flour ether are added and the mixture is made up to 1000parts with water.

The printing paste obtained is applied by a conventional printingprocess (roller, screen or rotary printing process) to an absorbent webof paper, approximately 15 kg. printing paste being used per 100 sq. m.paper. The printed paper is dried in a current of air heated toapproximately 100°.

Transfer printing is carried out on a cylinder heated to 180° over whichthe printed paper, with the printed side facing away from the cylinderand covered by the web of polyester fabric, runs. The paper and thepolyester web are left on the heated cylinder for 60 seconds duringwhich time the dye is sublimed off the paper and penetrates into thepolyester fibres. A transfer print with notable fastness properties isobtained.

Prints of high quality can also be obtained on material consisting ofsynthetic polyamides and cellulose acetates using the same process.

What is claimed is:
 1. A styryl dye compound of formula I, ##STR33## inwhich R₁ signifies (C₁₋₆) alkyl or (C₅₋₆) cycloalkyl,R₂ signifies (C₁₋₄)alkyl; or (C₁₋₄) alkyl monosubstituted by chlorine, bromine, phenyl,phenoxy, (C₁₋₄)alkoxy, (C₁₋₄)alkoxycarbonyl, (C₁₋₄)alkylcarbonyloxy,(C₁₋₄) alkoxycarbonyloxy or benzoyloxy, R₃ signifies hydrogen and (C₁₋₆)alkylsulphonyl, (C₅₋₆) cycloalkylsulphonyl, benzylsulphonyl di-(C₁₋₄)alkylaminosulphonyl or N-(C₁₋₄) alkyl-N-phenylaminosulphonylany phenylmoiety in such substituents R₂ and R₄ being unsubstituted or substitutedby up to two substituents selected from the group consisting ofchlorine, bromine, methyl and methoxy, or monosubstituted by ethoxy. 2.A compound according to claim 1, in which R₁ signifies an alkyl radical.3. A compound according to claim 2, in which R₁ signifies (C₂₋₄) alkyl.4. A compound according to claim 3, in which R₂ signifies alkyl or alkylmonosubstituted by chlorine, bromine, methoxy, ethoxy, phenyl, phenoxy,acetoxy, propionyloxy, (C₁₋₄)alkoxycarbonyl or (C₁₋₄)alkoxycarbonyloxy.5. A compound according to claim 3, in which R₂ signifies (C₂₋₄)alkyl;(C₂₋₄)alkyl monosubstituted by chlorine, bromine, methoxy, ethoxy,phenyl, phenoxy, acetoxy, propionyloxy, (C₁₋₄)alkoxycarbonyl or (C₁₋₄)alkoxycarbonyloxy; or benzyl.
 6. A compound according to claim 5, inwhich R₄ signifies (C₁₋₄) alkylsulphonyl, (C₅₋₆) cycloalkylsulphonyl,dimethyl- or diethylaminosulphonyl or benzylsulphonyl.
 7. A compoundaccording to claim 6, in which R₄ signifies (C₁₋₄) alkylsulphonyl,cyclohexylsulphonyl, benzylsulphonyl, or dimethyl- or diethylamino--sulphonyl.
 8. A compound according to claim 7, of formula Ia, ##STR34##in which R₆ signifies (C₂₋₄) alkyl,R₇ signifies (C₂₋₄) alkyl which isunsubstituted or monosubstituted by (C₁₋₂)alkylcarbonyloxy,(C₁₋₂)alkoxycarbonyl or (C₁₋₂)alkoxycarbonyloxy, R₈ signifies (C₁₋₄)alkylsulphonyl, cyclohexylsulphonyl, benzylsulphonyl, or di-(C₁₋₂)alkylaminosulphonyl.
 9. A compound according to claim 8, in which R₆signifies ethyl.
 10. A compound according to claim 9, in which R₇signifies an unsubstituted or substituted ethyl radical.
 11. A compoundaccording to claim 8, in which R₇ signifies unsubstituted (C₂₋₄) alkyl.12. A compound according to claim 8, in which R₈ signifies(C₁₋₄)alkylsulphonyl, cyclohexylsulphonyl or benzylsulphonyl.
 13. Acompound according to claim 12, of formula Ib, ##STR35## in which R₉signifies (C₁₋₄) alkylsulphonyl, cyclohexylsulphonyl, orbenzylsulphonyl.
 14. A compound according to claim 12, of formula,##STR36##
 15. A compound according to claim 12, of formula, ##STR37##16. A compound according to claim 12, of formula, ##STR38##
 17. Acompound according to claim 8, of formula, ##STR39##
 18. A compoundaccording to claim 12, of formula, ##STR40##
 19. A compound according toclaim 7 wherein R₄ is (C₁₋₄)alkylsulphonyl, benzylsulphonyl orcyclohexylsulphonyl.
 20. A compound according to claim 1 whereinR₁ isalkyl and R₄ is (C₁₋₄)alkylsulphonyl, benzylsulphonyl orcyclohexylsulphonyl.